Chlorination of hydrocarbon gases



E. H. PAYNE ET AL CHLORINATION OF HYDROCARBON GASES Original Filed Aug. 18, 1920 the pipe 11, from which it passes thru the Patented Dec. 23, 1924.

UED STATES PATENT OFFICE. v

ELMER H. PAYNE AND SAMUEL A. MONTGOMERY, OF WOOD RIVER, ILLINOIS, AS-

SIGNORS TO STANDARD OIL COMPANY, OF WHITING, INDIANA, A CORPORATION OF INDIANA.

CHLORINATION OF HYDROCARBON GASES.

Original application'filed August 18-, 1920, Serial No. 404,318. Divided and this application filed February 19, 1923. Serial No. 619,932.

To all whom it may concern:

Be it known that we, ELMER H. PAYNE and SAMUEL A. MONTGOMERY, citizens of the United States, residing at Wood River, in the county of Madison and State of Illinois,

have invented a new and useful Improvementin Chlorination of Hydrocarbon Gases, of which the following is a specification.

The present invention relates to the chlorination of gaseous hydrocarbons, and more particularly of those present in the gases produced by the distillation of high boiling point hydrocarbons under pressure for the production of low boiling hydrocarbon oils such as gasoline. It will be fully understood from the following description thereof, illustrated by the accompanying drawing, in which apparatus suitable for carrying out the invention is illustrated.

. Referring more particularly to the drawings, the numeral 5 indicates the chlorination chamber, which may consist of a central reaction chamber 6, of lead or other suitable inert material such as stone ware, and which is surrounded by a heating coil 7 and an external jacket 8. The gas which is to be chlorinated is drawn from a suitable gas holder or main (not shown) and enters the e trap 10. It issues from the trap 10 thru valved pipe 12, the flow-meter 13 and the pipe 14 to the trap 15. From the trap 15 it passes out thru pipe 16 provided with valve 17 to the humidifier 18. A suitable pressure gauge 19 is provided on the line 16. In the humidifier 18 the gas takes up moisture, and the moist gas passes out of the humidifier'thru the pipe 20 provided with a valve 21 and the pipe 22 provided with check valve 23 and valves 24 and 25 to the small pipe 26 which is connected upon the one hand to the pressure gauge 27 and upon the other to a fork 28 of the tube 29'leading downwardly thru the jacket 8 into the lower portion of the reaction chamber 6. A by-pass for gas from the trap 10 to the reac-' tion chamber is provided by the pipe 30 which connects with the pipe 11 leading from trap 10 with the pipe 22. The pipe 30 .is provided with a valve 31 near its point of connection with the pipe 11 and with a valve system thru the pipes 9, which lead it into, 1;

chamber thru this by-pass, the trap 15, the meter 13, and the humidifier 18 are cut off by closmgthe'valve in pipe 12 and the valve 21 111 plpe 20. Means are likewise provided for introducing the gas directly into the bottom of the reaction chamber, in which case the valve 17 in the pipe 16 is closed and the gas passes from the pipe16 thru the valved pipe 33'into the humidifier 34, from which it issues thru the pipe 35 provided with check valve 36 into thepipe 37 connected to the trap 38. From the trap 38 it passes up thru valve pipe 39, into the bottom of the reaction chamber 6. A pressure gauge 40 is provided on line 37. Chlorine, which may sultably be supplied in a tank 41, passes therefrom thru pipe 42, flow-meter 43 and pipe 44 to the other fork 45 leading into the tube 29, Which carries the chlorine to the bottom of the reaction chamber.

Vapors issuing from the reaction chamber thru pipe 46 pass thru the coils of transparent quartz or glass tubing 47, in which they are exposed to the light rays from a suitable light source such as the mercury vapor are 48, and subsequently pass on thru a succession of scrubbers 49, 49, in which they deposit the liquid chlorinated products, which collect in the receptacles 50, 50.

The gaseous products of chlorination pass on thru pipes 51 to any suitable low temperature condensing or compressing system adapted for their recovery.

In carrying out the present invention, a. suitable catalyst is first preparedwhich is capable of accelerating the chlorination of the gas and which is not affected nor poisoned by the materials undergoing reaction or their products. This catalyst may be prepared in any suitable reaction chamber; it is preferred, however, to prepare it in the reaction chamber 6 in which the chlorination of the gas is subsequently to be effected.

To prepare the catalyst the internal reaction chamber 6 may be filled about two thirds full of high boiling point oil, for example, a parafline distillate having an initial boiling point of about 450 F. The oil is then heated by means of the steam coils 7' carrying steam at desired pressure, and chlorine is then passed therethru, its rate being controlled to maintain the temperature of the 32 near its point of connection with the pipe oil at about 300 F. At the same time a 22. When gas is passed to the reaction relatively small proportion of gas is confollowing results: t

Percent.

Chlorine by weight 19.16

=Ash by weight 3.22

ber. The chlorine is supplied slowly, to'prcrent excessive rise in temperature of the oil. The passage of the chlorine is continued until the catalyst substantially ceases evolving hydrochloric acid. At this point the product in the reaction chamber is a solid mass resembhng 6031111 1ts colorand fracture. It 15 exceedingly porous, it. being foundon dis placement with water that one gram of the catalystcontains approxin'iately to 4 cubic centimeters of air. An average analysis ofthe products thus obtained gives the Carbon-disulphid soluble by weight 21.90

Carbon tetrachloride soluble by weight 1 17.20

Hexane soluble 16.89

Substantially all of the chlorine present in the catalyst appears to be in thecombined form.

The preparation of the catalyst has'been" The catalyst may likewise be formed in a separate container, comminuted and introduced as a powder into the internal reaction chamber 6. An opening 52 provided with a suitable removable plug is provided for this purpose.

After the reaction chamber 6 has been completely charged with the completed catalyst, the by-pass line in the gas supply is closed by closing valves 31 and 32, an

order that the incoming gas may travel thru the meter 13, the traps 15, and the humidifier 18 before it enters the reaction chamber thru the tubes 29. The gas employed is, in the present example, a pressure still'gas containing a lower proportion of methane and a higher proportion of unsaturated components than natural gas. Other still gases or natural gas or mixtures of the hydrocarbon gases may, however, be employedl At the same time chlorine is introduced thru the meter 43 and the pipes 44. If desired, the gas, instead of being introduced use of suitable freezing mixtures.

thru the tube 29, may be diverted from the humidifierlS by closing valve 17 and caused to travel thru humidifieri-land trap 38 into the bottom of the reaction chamber.

The relative proportions of chlorine. and gas introduced into the reaction chamber are preferably three to one by volume. \Vith this proportion, the most satisfactory yield of liquid chlorinated products is found to be produced. The temperature of the reaction chamber is controlled by the use of steam at desired pressure: in the coils 7 to maintain the temperature within the reaction chambeer at about 300 F The products escaping from the reaction chamber pass thru the pipe 46 into the tubing 47, in which a further chlorination results by reason of the influence of the light rays from a suitable light source -18, indicated as a mercury vapor :arc. This further chlorination goes smoothly and without explosive violence, and the prod- I note of the complete chlorination process are passed thruscrubbers 49, 49. the liquid product collecting in the receptacles 50, 50. The gaseous products issue thru the pipe 51. This'issui'ng gas is found to contain methyl chloride. .This may betcondensed by the The chlorinated products maybe refined bytreatment with caustic soda to removehydrochloric acid and traces of chlorine, and steam distillation. tilllate is water white and has an agreeable oc or. 1.364, its initial boiling pointis about 13t'F. and its dry point about 380 F.

lVith the proportions of chlorine and gas above described, the chlorine is almost completely combined with the gas in the course of the reaction. Notwithstanding the relatively high proportion of higher hydrocarbons and of unsaturated hydrocarbons in the gases treated, as compared with those present in natural gas, substantially no solid compounds such as hexachlorethane, were found'under the conditions of reaction de scribed, even when the proportion of chlorine to gas was increased greatly above the proportion of three to one.

This application is a division of our prior d application 404,318 filed August 18th, 1920. the valves in lines 12 and 2-0 are opened in .chlorine and hydrocarbon gases in the presence of a porous catalyst comprising chlorinated hydrocarbon ,material at about After. such treatment the 1 dis- I Its specific gravity approximates 300 F., and exposing the resulting products to light rays to complete the chlorination.

3. The process of chlorination which consists in simultaneously bringing together chlorine and hydrocarbon gases in the proportion of three volumes of chlorine to one volume of gas in the presence of a porous catalyst comprising chlorinated hydrocarbon material at about 300 F.

4. The process of chlorination which consists in simultaneously bringing together in the absence of light chlorme and hydrocarbon gases in the presence of a porous catalyst comprising chlorinated hydrocarbon material at about 300 F.

5. The liquid chlorinated product resulting'from the chlorination of the hydrocarbons of pressure still gases at 300 F., alkali treatment and distillation, and having a specific gravity approximating 1.364 and a distillation range of about 134 F. to about ELMER H. PAYNE. SAMUEL A. MONTGOMERY. 

